JP2009067692A - PROCESS FOR PRODUCING FLUORINE-CONTAINING ALKYLSULFONYLAMINOETHYL alpha-SUBSTITUTED ACRYLATES - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for synthesizing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates under mild conditions using a solvent being friendly to the environment. <P>SOLUTION: A sulfonamidation reaction of an aminoethyl α-substituted acrylate or a salt thereof with a fluorine-containing alkylsulfonyl fluoride is carried out in the presence of a base. In the process, the reaction is carried out by using a fluorine-containing compound as a solvent. 1,1,2,2,3,3,4-Heptafluorocyclopentane, trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene etc., are particularly preferable as the fluorine-containing compound. The reaction proceeds with a sufficient conversion rate and selectivity even mild conditions, e.g. ≥0°C by adopting the solvents, which results in the production of the objective substance in high yield. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates represented by the general formula [3] which are compounds useful as monomers corresponding to next-generation photoresists.

[Wherein R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trimethyl group, It is a fluoromethyl group or a perfluoroethyl group, and R ² is a fluorine-containing alkyl group having 1 to 6 carbon atoms. ]
It relates to the manufacturing method.

  Sulfonylaminoethyl α-substituted acrylates are promising compounds as monomers for next-generation resist materials, and resists containing such monomers as constituent elements are known to have excellent light transmission and surface adsorption properties. (Patent Document 1).

  In Patent Document 1, there is no detailed description regarding the synthesis of the fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates represented by the above general formula [3], which is the target compound of the present invention, and sulfonylaminoethyl α in a broad concept. It is described that -substituted acrylates can be synthesized by condensation of the corresponding sulfonylaminoethanol and α-substituted acrylic acid chloride.

  However, according to Patent Document 2, the above-described method is difficult to apply for the synthesis of fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates, and as a means for solving this, the general formula [1a] or [ 1b] is reacted with a fluorine-containing alkylsulfonic acid halide or fluorine-containing alkylsulfonic acid anhydride, and the fluorine-containing alkylsulfonylaminoethyl α represented by the general formula [3] is reacted. A technique for synthesizing substituted acrylates is shown. Here, acetonitrile is used as a reaction solvent (the following scheme).

  Also, Patent Document 3 discloses a technique for synthesizing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates by reacting fluorine-containing alkylsulfonic acid chloride and aminoethyl α-substituted acrylate. There, methylene chloride is used as a reaction solvent (the following scheme).

U.S. Pat.No. 6,165,678 JP 2005-281301 A U.S. Patent No. 694932

  The methods employed in Patent Document 2 and Patent Document 3 are excellent methods for synthesizing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates, but have the following problems.

  First, methylene chloride used as a reaction solvent in Patent Document 3 is an excellent solvent that enables a reaction under mild conditions, but is a harmful substance and must be handled in a closed system, so it is a large scale. To use in, it becomes a load.

  On the other hand, in Patent Document 2, acetonitrile, which is easy to obtain and handle, is used as a solvent and succeeds in obtaining the target product. In particular, it has been shown that when a reaction is carried out using a fluorine-containing alkylsulfonic acid fluoride that is easily available in large quantities, the target product can be produced in a significantly high yield.

  However, although the method of Patent Document 2 is an advantageous method, there is a problem that the reaction is carried out under a strong cooling condition of “−30 ° C. to −50 ° C.”. That is, cooling to −30 ° C. in a large-capacity reactor is costly due to problems with equipment, refrigerants, etc., and becomes a burden for industrialization on a large scale. If the reaction can be carried out at a temperature close to 0 ° C., it will be much more advantageous for obtaining the target substance on a large scale.

  However, in the method of Patent Document 2, the reaction temperature is set to around 0 ° C., and the above-mentioned aminoethyl α-substituted acrylate or a salt thereof is used as a raw material, and the fluorinated alkylsulfonylaminoethyl α- When synthesis of substituted acrylates was attempted, it was found that the yield of the target product was significantly reduced as compared with the case of performing the reaction at -30 ° C. or less (Comparative Example 1). In this case, since the content of the target product in the reaction mixture is also reduced, the purification load is also increased.

  Note that the yield of the target product decreases as the temperature rises because the fluorine-containing alkylsulfonic acid fluoride represented by the general formula [2] having volatility cannot be sufficiently dissolved in the liquid phase. It is considered as a cause. For this reason, this inventor also tried performing the said reaction on pressurization conditions. However, at an elevated temperature of around 0 ° C., no improvement in yield was observed even if the reaction was carried out under pressurized conditions (Comparative Example 2).

  Thus, although it is possible to synthesize the fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate represented by the general formula [3] based on the conventional technique, The challenge was to find a method for efficient synthesis under mild conditions (higher temperatures).

  In view of the problems of the prior art, the present inventors have intensively studied to establish a method for producing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates suitable for production on an industrial scale.

  As a result, an α-substituted acrylate represented by the general formula [1a] obtained by neutralizing a salt of aminoethyl α-substituted acrylate or a salt of α-substituted acrylate with a base

(The meaning of R ¹ in the formula [1a] is the same as described above.) In the fluorine-containing alkylsulfonic acid fluoride represented by the formula [2]

In the reaction with “a compound containing fluorine”, a remarkable increase in the reactivity occurs, and the target general purpose is obtained in a high yield without using a low temperature of −30 to −50 ° C. The inventors have found that fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates represented by the formula [3] can be obtained, and have completed the present invention.

  That is, the present invention includes [Invention 1] to [Invention 9] and provides a novel method for producing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates.

  [Invention 1] Aminoethyl α-substituted acrylate represented by the general formula [1a]

A fluorine-containing alkylsulfonic acid fluoride represented by the general formula [2]

Or a salt of aminoethyl α-substituted acrylate represented by the general formula [1b]

Is reacted with a fluorine-containing alkylsulfonic acid fluoride represented by the general formula [2] in the presence of a base, and a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate represented by the general formula [3]

A method of manufacturing
A method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate, wherein the reaction is carried out using a fluorine-containing compound as a solvent.
[Wherein R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trimethyl group, A fluoromethyl group or a perfluoroethyl group, R ² is a fluorine-containing alkyl group having 1 to 6 carbon atoms, X ⁿ⁻ is a counter anion (where n is a positive integer), and Y is fluorine An atom, a chlorine atom, or a bromine atom. ]
[Invention 2] The fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to Invention 1, characterized in that, in Invention 1, the fluorine-containing compound is a compound having one or more trifluoromethyl groups. Manufacturing method.

  [Invention 3] In Invention 1, the fluorine-containing compound is 1,1,2-trichloro-2,2-difluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,1,2-trichloro-2- Fluoroethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 2-chloro-1,1,2-trifluoroethyl = Ethyl = ether, 2-chloro-1,1,2-trifluoroethyl = methyl = ether, ethyl = 1,1,2,2-tetrafluoroethyl = ether, 1,1,3,3,3-penta Fluoropropyl = methyl = ether, heptafluoropropyl = 1,2,2,2-tetrafluoroethyl = ether, 1,1,1,2,3,3-hexafluoropropyl = methyl = ether, 1,1,1 , 2,3,3-Hexafluoropropyl = 2,2,2-trifluoroethyl ether, 1- (methoxy) nonafluorobutane, 1- (ethoxy) nonafluorobutane, methyl trifluoroacetate, trifluoro Ethyl acetate, n-butyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, methyl perfluoropentanoate, ethyl perfluoropentanoate, methyl perfluoroheptanoate, ethyl perfluoroheptanoate, perfluorooctane Methyl acetate, ethyl perfluorooctanoate, methyl perfluorononanoate, ethyl perfluorononanoate, methyl 2,3,3,3-tetrafluoropropionate, ethyl 2,3,3,3-tetrafluoropropionate, acetic acid 2,2,2-trifluoromethyl, 2,2,2-trifluoromethyl butanoate, trifluoromethylbenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, 2,4 -Dichlorobenzotrifluoride, fluorobenzene, 1,2-difluorobenzene, 1, 3-difluorobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, pentafluorobenzene, hexafluorobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 1,2-dichloro Hexafluorocyclobutane, perfluorodimethylcyclobutane, 1,2-dichlorohexafluorocyclopent-1-ene, 1,1,2,2,3,3,4-heptafluorocyclopentane, octafluorocyclopentane, perfluoromethyl Cyclohexane, perfluoro-1,2-dimethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoroethyldimethylcyclohexane, perfluoroalkane compounds represented by the following formula

(Where x is an integer of 4 to 20) and a perfluoroalkylamine compound represented by the following formula:

 (Wherein y is an integer of 1 to 20), the fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to the invention 1, which is at least one compound selected from the group consisting of Manufacturing method.

  [Invention 4] The process for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to any one of Inventions 1 to 3, wherein the temperature of the reaction is −25 ° C. to 50 ° C.

  [Invention 5] The invention according to any one of Inventions 1 to 4, wherein the amount of the fluorine-containing compound used as a solvent is 0.05 to 20 g with respect to 1 g of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt. Of producing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates.

  [Invention 6] Base is trimethylamine, triethylamine, N, N-diethylmethylamine, tripropylamine, tributylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, water The method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to any one of Inventions 1 to 5, which is at least one base selected from the group consisting of potassium oxide.

[Invention 7] Production of fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to any one of Invention 1 to Invention 6, wherein R ¹ is a methyl group and R ² is a trifluoromethyl group. Method.

  [Invention 8] The fluorine-containing alkylsulfonylamino according to any one of Inventions 1 to 7, characterized in that, in addition to the fluorine-containing compound, a “solvent containing no fluorine atom” is allowed to coexist as a solvent. A method for producing ethyl α-substituted acrylates.

  [Invention 9] The group “a solvent not containing a fluorine atom” is composed of acetonitrile, benzonitrile, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, dimethylsulfoxide, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, triethylamine, and pyridine. The method for producing a fluorinated alkylsulfonylaminoethyl α-substituted acrylate according to Invention 8, which is at least one compound selected from the group consisting of:

  According to the present invention, the desired fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates can be produced in a significantly higher yield than before under mild conditions. Therefore, the present invention is a very excellent method for producing fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates on an industrial scale.

  Hereinafter, the present invention will be described in more detail.

[Ingredients and objects]
The substituent R ¹ of the target compound represented by the general formula [3] targeted by this reaction is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl. Group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, or a perfluoroethyl group.

R ² is a fluorine-containing alkyl group having 1 to 6 carbon atoms, and a fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl, n-perfluoropropyl group, n-perfluorobutyl and the like are preferable.

The compounds represented by the general formulas [1a], [1b] and [2] as raw materials depend on the types of substituents R ¹ and R ^{2 in} the target fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate. Just choose.

In the present invention, it is particularly preferable that R ¹ is a methyl group and R ² is a trifluoromethyl group in view of the usefulness of the product.

Further, the counter anion X ⁿ⁻ in the general formula [1b] is not particularly limited as long as it is an inert ion that does not affect the reaction, but a monovalent or divalent anion in which n is 1, 2 or 3 Are particularly preferred, and examples thereof include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, perbromate ion, hydrogen sulfate ion, sulfate ion, phosphate ion and the like.

  These compounds represented by the general formulas [1a] and [1b] can be synthesized by the method described in Patent Document 2, for example.

The reaction of the present invention can be carried out in a batch reactor.
Although the conditions are described below, it does not prevent each reaction apparatus from changing the reaction conditions to an extent that can be easily adjusted by those skilled in the art.

The salt of aminoethyl α-substituted acrylate represented by the general formula [1b] of the raw material to be used can be synthesized by adding a carboxylic acid chloride such as methacrylic acid chloride to the hydrochloride of aminoethanol. The aminoethyl α-substituted acrylate represented by the general formula [1a] can be obtained by treating a salt of aminoethyl α-substituted acrylate obtained by the above-described method with a base (Patent Document 2).
The fluorine-containing alkylsulfonic acid fluoride used as the other raw material can be obtained by electrolytic fluorination of the corresponding alkylsulfonic acid fluoride ("Fluorine compound", page 76 (1979, Kodansha Scientific) ).

[About Base]
In the case of using free aminoethyl α-substituted acrylate represented by the general formula [1a] as a raw material, the progress of the reaction is observed even if no base is present. In the presence of

  Bases include trimethylamine, triethylamine, N, N-diethylmethylamine, tripropylamine, tributylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide. At least one member selected from the group is preferably used. Of these, triethylamine is particularly preferred because of its high reactivity.

  In addition, when a salt of aminoethyl α-substituted acrylate represented by the general formula [1b] is used as a raw material in the reaction of the present invention, a base is required.

  Bases used include trimethylamine, triethylamine, N, N-diethylmethylamine, tripropylamine, tributylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, water At least one selected from the group consisting of potassium oxide is preferably used. Of these, triethylamine is particularly preferred because of its high reactivity.

  Protic bases such as ammonia, primary amines and secondary amines can also be used as bases, but these bases react with fluorine-containing alkyl sulfonic acid fluorides to produce the corresponding amides. This is not preferable because the yield of the product may be reduced.

  When the aminoethyl α-substituted acrylate represented by the general formula [1a] is used as a raw material, the amount of the base used is usually 0.2 to 15.0 mol with respect to 1.0 mol of aminoethyl α-substituted acrylate as a substrate, and 0.5 -10.0 mol is preferable and 1.0-3.0 mol is more preferable. If the amount of the base is less than 0.2 mol with respect to 1.0 mol of the aminoethyl α-substituted acrylate as the substrate, both the selectivity of the reaction and the yield of the target product decrease, and if it exceeds 15.0 mol, the amount of the base not involved in the reaction increases. Therefore, it is not preferable economically. An excessive amount of inexpensive triethylamine or the like can be used to serve as a “solvent not containing fluorine atoms (described later)”, but in this case, the amount used may exceed 15.0 mol.

  When the aminoethyl α-substituted acrylate salt represented by the general formula [1b] is used as a raw material in the reaction of the present invention, the amount of the base used is 1.0 mol of the substrate aminoethyl α-substituted acrylate salt. In general, the amount is 0.5 to 30.0 mol, preferably 0.8 to 15.0 mol, and more preferably 1.5 to 5.0 mol.

  If the amount of the base is less than 0.5 mol relative to 1.0 mol of the aminoethyl α-substituted acrylate salt of the substrate, both the selectivity of the reaction and the yield of the target product will decrease, and if it exceeds 30.0 mol, the amount of the base not involved in the reaction will increase. This is economically undesirable.

  In addition, although cheap triethylamine etc. can be used excessively and it can also serve as a "solvent which does not contain a fluorine atom (after-mentioned)", the usage-amount may exceed 30.0 mol in this case.

  The amount of the fluorine-containing alkyl sulfonic acid fluoride used in the present invention is usually 0.2 to 3.0 mol, preferably 0.5 to 1.5 mol, preferably 0.9 to 1.0 mol of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt. -1.2 mol is more preferable.

  If the amount of fluorine-containing alkyl sulfonic acid fluoride is less than 0.2 mol with respect to 1.0 mol of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt, both the selectivity of the reaction and the yield of the target product decrease, exceeding 3.0 mol. Fluorine-containing alkylsulfonic acid fluoride that does not participate in the reaction is increased, which is economically undesirable from the point of disposal.

  This reaction also has a great advantage in that the reaction proceeds smoothly without excessively increasing one of the reaction substrates. In order to make use of such features of the present invention, the amount of the fluorine-containing alkylsulfonic acid fluoride is preferably 0.9 to 1.2 mol with respect to 1.0 mol of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt, In particular, the molar ratio between the two is preferably close to 1: 1.

[About solvent]
Next, the solvent which is an important component of the present invention will be described. The present invention is characterized in that the reaction is carried out using a fluorine-containing compound as a solvent. The fluorine-containing compound is not particularly limited as long as it is generally recognized as a fluorine-based solvent, but “a compound having one or more trifluoromethyl groups” is easily available. It is preferable because it is stable as a compound.

  Examples of the fluorine-containing compound including the above compounds include 1,1,2-trichloro-2,2-difluoroethane, 1,1-dichloro-2,2-difluoroethane, and 1,1,2-trichloro which are fluorocarbon compounds. -2-fluoroethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 2-chloro, a fluorine-containing ether compound -1,1,2-trifluoroethyl = ethyl ether, 2-chloro-1,1,2-trifluoroethyl = methyl ether, ethyl = 1,1,2,2-tetrafluoroethyl ether, 1 , 1,3,3,3-pentafluoropropyl = methyl ether, heptafluoropropyl = 1,2,2,2-tetrafluoroethyl ether, 1,1,1,2,3,3-hexafluoropropyl = Methyl = ether, 1,1,1,2,3,3-hexafluoropropyl = 2,2,2-trifluoroethyl = ether, 1- (methoxy) nonafluorobutane, 1- (ethoxy) nonaf Orobutane, fluorine-containing ester compounds such as methyl trifluoroacetate, ethyl trifluoroacetate, n-butyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, methyl perfluoropentanoate, ethyl perfluoropentanoate, Methyl perfluoroheptanoate, ethyl perfluoroheptanoate, methyl perfluorooctanoate, ethyl perfluorooctanoate, methyl perfluorononanoate, ethyl perfluorononanoate, methyl 2,3,3,3-tetrafluoropropionate, Ethyl 2,3,3,3-tetrafluoropropionate, 2,2,2-trifluoromethyl acetate, 2,2,2-trifluoromethyl butanoate, trifluoromethylbenzene, a fluorine-containing aromatic compound, m -Bis (trifluoromethyl) benzene, p-bis (to Fluoromethyl) benzene, 2,4-dichlorobenzotrifluoride, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, pentafluoro Benzene, hexafluorobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, fluorine-containing cycloalkane compounds 1,2-dichlorohexafluorocyclobutane, perfluorodimethylcyclobutane, 1,2-dichlorohexafluoro Cyclopent-1-ene, 1,1,2,2,3,3,4-heptafluorocyclopentane, octafluorocyclopentane, perfluoromethylcyclohexane, perfluoro-1,2-dimethylcyclohexane, perfluoro-1 , 3-Dimethylcyclohexane, Perfluoroethyldimethylcyclohexane, represented by the following formula That perfluoroalkane compound

(Where x is an integer of 4 to 20, and preferably 4 to 10), and a perfluoroalkylamine compound represented by the following formula:

 (Here, y is an integer of 1 to 20, and preferably 2 to 5.) At least one compound selected from the group consisting of:

  Among the above fluorine-containing compounds, 1,1,2,2,3,3,4-heptafluorocyclopentane, trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoro) Methyl) benzene is particularly preferable because the yield is significantly improved when the reaction of the present invention is carried out at a moderate temperature of, for example, about 0 ° C. to room temperature.

  Of the fluorine-containing compounds, protic compounds such as fluorinated alcohols are not preferred because they may react with fluorine-containing alkyl sulfonic acid fluoride to produce sulfonic acid esters, thereby reducing the yield of the desired product. .

  In this reaction, the starting aminoethyl α-substituted acrylate salt is a solid, and after the reaction, a base halide is precipitated as a by-product. Even when only a fluorine-containing compound is used as a solvent, the reaction of the present invention proceeds well. However, when only a fluorine-containing compound is used, the above-mentioned solid is difficult to be uniformly dispersed in the reaction solution. Operation may be burdensome.

  Here, in addition to the above-mentioned fluorine-containing compound, the present inventors coexisted a “solvent not containing fluorine atoms” in the reaction system and used it as a “mixed solvent”, whereby “fluorine-containing compound was used as a solvent”. It was found that the operability can be remarkably improved without substantially impairing the “reaction promoting effect”.

  “A solvent that does not contain fluorine atoms” refers to nitrile solvents such as acetonitrile and benzonitrile, amide solvents such as dimethylformamide, dimethylacetamide, and dimethylimidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, diethyl ether, diisopropyl ether, di Ether solvents such as butyl ether and tetrahydrofuran; basic solvents such as triethylamine, trimethylamine, tripropylamine, tributylamine and pyridine; halogenated solvents such as methylene chloride, chloroform and carbon tetrachloride; aromatics such as benzene, toluene and xylene It is at least one compound selected from a series hydrocarbon solvent, pentane, hexane, and heptane.

  Protic compounds such as water, alcohol, ammonia, and primary and secondary amines are not preferable because they may react with the fluorine-containing alkylsulfonic acid fluoride to reduce the yield of the target product.

  Among the "solvents not containing fluorine atoms", nitrile solvents such as acetonitrile and benzonitrile, amide solvents such as dimethylformamide, dimethylacetamide and dimethylimidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, diethyl ether, diisopropyl ether In particular, ether solvents such as dibutyl ether and tetrahydrofuran, and basic solvents such as triethylamine and pyridine are particularly suitable because they have a large effect of improving the operability and have a low environmental impact.

  In the present invention, a liquid of the above bases (trimethylamine, triethylamine, N, N-diethylmethylamine, tripropylamine, tributylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, etc.) is reacted. Minimum amount (equivalent amount) required for the compound (ie, when aminoethyl α-substituted acrylate represented by the general formula [1a] is used as a raw material, the number of moles equal to the compound, the amino acid represented by the general formula [1b] When a salt of ethyl α-substituted acrylate is used as a raw material, when it is added in an amount exceeding 2 times the number of moles of the salt, these bases also serve as a “solvent that does not contain fluorine atoms”. I also serve.

  In the solvent used in this reaction, when a mixture of the above fluorine-containing compound and “a solvent not containing a fluorine atom” is used, the content of the fluorine-containing compound in the whole solvent is usually 5% to 80%, % To 70% is preferable, and 30% to 60% is particularly preferable. If it is less than 5%, the effect of improving the reactivity by using a fluorine-containing compound as a solvent is small, which is not preferable. If it exceeds 80%, the effect of improving the operability due to the coexistence of the “solvent containing no fluorine atom” becomes small.

The amount of the fluorine-containing compound used as a solvent used in this reaction is usually 0.05 to 20 g, preferably 0.5 to 10 g, based on 1 g of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt as a raw material. 2-5g is more preferable.
If it is less than 0.05 g, the effect of improving the reactivity by using a fluorine-containing compound as a solvent is small, and if it exceeds 20 g, it is not economically preferable from the viewpoint of productivity.

[Reaction temperature]
There is no particular limitation on the reaction temperature when carrying out this reaction. However, the present invention is advantageous in that “the target product can be obtained in a high yield even when the reaction is carried out at a temperature higher than −30 ° C. by using a fluorine-containing compound as a solvent”. Therefore, the reaction temperature in the present invention is usually −25 to 50 ° C., preferably −20 to 30 ° C., and particularly preferably −10 ° C. to room temperature (25 ° C.). In the initial stage of the reaction, it is particularly preferable to control to −10 ° C. to 20 ° C.

  At −30 ° C. or lower, the reaction itself proceeds suitably, but as described above, it is not desirable because of the cost of cooling from an industrial viewpoint.

  On the other hand, when the temperature exceeds 50 ° C., the raw material aminoethyl α-substituted acrylate, aminoethyl α-substituted acrylate salt or product fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate is easily polymerized.

[About the reactor]
The reactor for carrying out the reaction is preferably a reactor made of tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass or the like, a glass container, or stainless steel.

  This reaction can be performed in an inert gas atmosphere, but even if the reaction is performed in the air, no significant difference is observed between the reaction in the inert gas atmosphere and the synthesis is performed particularly on a large scale. In some cases, it is preferable in terms of cost to perform the reaction in the atmosphere.

  This reaction is sulfonamidation, and it is not preferable that water or a protic compound is mixed into the reaction system to such an extent that the reaction is inhibited. In order to prevent this, it is desirable to use a dehydrated “compound containing no fluorine atom” and “compound containing a fluorine atom” used as a solvent. The water content allowed in the solvent compound and the content of the protic compound vary depending on the amount of the solvent used in the reaction, but are preferably 0.3% or less, more preferably 0.05% or less.

  Since the reaction of the present invention does not require any pressurizing condition, a reactor for normal pressure can be suitably used. On the other hand, the reaction can be carried out by using a pressure-resistant reactor and sealing the inside of the system. In addition, even when carried out under pressurized conditions, the yield is hardly improved, but when producing the target product on a large scale, it may be advantageous to carry out the reaction in a closed system because it is easy to control. .

[Examples of desirable embodiments]
Although the method for carrying out the present invention is not limited, details will be described with respect to an example of a desirable embodiment.

  A base, a solvent, a raw material aminoethyl α-substituted acrylate salt and a polymerization inhibitor are added to a reactor that can withstand the reaction conditions, and the raw material mixture is cooled with a refrigerant while stirring.

  After the temperature of the mixture becomes constant, a predetermined amount of fluorine-containing alkyl sulfonic acid fluoride is added to the reaction mixture.

  It is preferable to monitor the production of the target product by sampling or the like, confirm that the increase in the production amount of the target product has stopped, and set the end point of the reaction.

  The reaction time of this reaction cannot be determined unconditionally because the reactivity changes depending on the base, solvent, substrate, and fluorine-containing alkylsulfonic acid fluoride used, but it is 0.5 to 12 hours, 1 to 6 hours 2 hours to 4 hours is more preferable. The reaction is in progress within 0.5 hour, and when the reaction is terminated here, the yield decreases, which is not desirable. Further, even if the reaction is continued for more than 12 hours, the substantial reaction is completed, and an effect such as an increase in yield is not recognized. However, there is no particular problem even if the reaction is continued for more than 12 hours due to the manufacturing process such as the time schedule.

  The fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates represented by the general formula [3] produced by the method of the present invention are purified by applying a known method. For example, the reaction solvent is distilled off under reduced pressure. The crude organic compound is obtained by suspending in a solvent such as diisopropylpropyl ether, filtering off the precipitated hydrogen halide salt and distilling off the solvent.

  The obtained crude organic matter can be purified by column chromatography, distillation, recrystallization and the like to obtain high-purity fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not restricted to these embodiments.
Here, “%” of the compositional analysis value is a solvent component obtained by collecting a part of the reaction mixture or product and measuring an organic component dissolved in diisopropyl ether by gas chromatography. "Area%" of organic components excluding.

[Example 1]
200 g of acetonitrile, 200 g of 1,1,2,2,3,3,4-heptafluorocyclohexane (HFCPA) in a 2 L (liter) three-necked flask equipped with a thermometer, reflux condenser and calcium chloride tube, triethylamine 134.7 g (1.33 mol) and 2-aminoethyl 2-methylacrylate hydrochloride 100.0 g (0.6 mol) were added and cooled to 0 ° C. with stirring.

  After the internal temperature reached 0 ° C., 101.3 g (0.66 mol) of trifluoromethanesulfonic acid fluoride was introduced into the slurry by gas so as not to exceed 10 ° C. After the introduction, the temperature was raised to room temperature (25 ° C., hereinafter the same in the present specification) with stirring.

  300 g of clean water was added to the reaction solution, and the mixture was stirred for 30 minutes and then separated into two layers. The aqueous layer was removed, dilute sulfuric acid (a mixture of 10 g of sulfuric acid and 300 g of clean water) was added and stirred for 30 minutes, and the two layers were separated to remove the aqueous layer. Further, sodium bicarbonate water (a solution in which 10 g of sodium hydrogen carbonate was dissolved in 300 g of tap water) was added, and the same operation was performed to obtain an organic layer.

  After distilling off the solvent under reduced pressure, the resulting crude product was dissolved in a mixed solvent of isopropyl ether and heptane by heating and cooling, and crystallization was performed by cooling. 111 g of 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. When the composition was examined by gas chromatography, the purity of the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 98.0%. The yield was 71%.

Melting point: 47-48 ° C., ¹ H NMR (solvent: CDCl ₃ , reference material: TMS); δ 6.16 (dq, J = 0.98 Hz, J = 1.22 Hz, 1H), 5.66 (dq, J = 1.46 Hz, J = 1.22Hz, 1H), 4.32 (dd, J = 5.12Hz, J = 1.71Hz, 2H), 3.61 (dt, J = 0.49Hz, J = 5.12Hz, 2H), 1.96 (dd, J = 0.98Hz , J = 1.46 Hz, 3H) ¹⁹ F NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-77.97 (s, 3F).

  Thus, in this example, synthesis was performed in a mixed solvent of both using HFCPA as the “fluorine-containing compound” and acetonitrile as the “solvent containing no fluorine atom”. As a result, although the temperature was 0 ° C. or higher, the target product could be obtained with a very good yield. During the reaction, the operability of the reaction liquid throughout the reaction was also good.

[Example 2]
300 g of HFCPA, 134.7 g (1.33 mol) of triethylamine, and 100.0 g (0.6 mol) of 2-aminoethyl 2-methylacrylate hydrochloride were placed in a 2 L three-necked flask equipped with a thermometer, reflux condenser, and calcium chloride tube. Cooled to 0 ° C. with stirring.

  After the internal temperature reached 0 ° C., 101.3 g (0.66 mol) of trifluoromethanesulfonic acid fluoride was introduced into the slurry by gas so as not to exceed 10 ° C. After the introduction, the temperature was raised to room temperature with stirring.

  300 g of clean water was added to the reaction solution, and the mixture was stirred for 30 minutes and then separated into two layers. The aqueous layer was removed, dilute sulfuric acid (a mixture of 10 g of sulfuric acid and 300 g of clean water) was added and stirred for 30 minutes, and the two layers were separated to remove the aqueous layer. Further, sodium bicarbonate water (a solution in which 10 g of sodium hydrogen carbonate was dissolved in 300 g of tap water) was added, and the same operation was performed to obtain an organic layer.

  After distilling off the solvent under reduced pressure, the resulting crude product was dissolved by heating in a mixed solvent of isopropyl ether and heptane, crystallized by cooling, and the resulting crystals were filtered and dried. 102 g of 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. When the composition was examined by gas chromatography, the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 97.8%. The yield was 65%.

  As described above, in this example, HFCPA was used alone as a solvent and the reaction was carried out. In this case as well, the target product could be obtained with a good yield of 65%.

[Examples 3 to 6]
Except for the temperature and solvent shown in Table 1, the same conditions as in Example 1 were used to synthesize 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate. The results are shown in Table 1.

  Thus, it was found that by using various fluorine-containing compounds as a solvent, the target product can be produced with a high yield of 66% to 74% despite the temperature of 0 ° C. or higher.

[Comparative Example 1]
200 g of acetonitrile and 200 g of diisopropyl ether, 134.7 g (1.33 mol) of triethylamine, 100.0 g of 2-aminoethyl 2-methylacrylate hydrochloride (0.6 mol) in a 2 L three-necked flask equipped with a thermometer, reflux condenser and calcium chloride tube The mixture was cooled to 0 ° C. with stirring.

  After the internal temperature reached the predetermined temperature, 101 g (0.66 mol) of trifluoromethanesulfonic acid fluoride was introduced into the slurry as a gas over one hour. After the introduction, the temperature was raised to room temperature with stirring.

  300 g of clean water was added to the reaction solution, and the mixture was stirred for 30 minutes and then separated into two layers. The aqueous layer was removed, dilute sulfuric acid (a mixture of 10 g of sulfuric acid and 300 g of clean water) was added and stirred for 30 minutes, and the two layers were separated to remove the aqueous layer. Further, sodium bicarbonate water (a solution in which 10 g of sodium hydrogen carbonate was dissolved in 300 g of tap water) was added and the same operation was performed to obtain an organic layer.

  After distilling off the solvent under reduced pressure, crystallization is performed by heating and dissolving in isopropyl ether and heptane, cooling, and the resulting crystals are filtered and dried to obtain high-purity 2-{[( 65.7 g of (trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. The yield was 42%.

  Thus, in this comparative example, the reaction is carried out at 0 ° C. to room temperature using “acetonitrile / diisopropyl ether mixed solvent (solvent system containing no fluorine)”. As a result, the yield was 42%, which was significantly lower than that of Reference Example 1 (reaction carried out at −30 ° C.).

[Comparative Example 2] Reaction under pressurized conditions 100 g of acetonitrile, 300 g of IPE, 134.6 g (1.33 mol) of triethylamine, 2-aminoethyl 2-methyl in a 1 L autoclave equipped with a thermometer, a gas blowing tube and a stirrer 100 g (0.6 mol) of acrylate hydrochloride was added and cooled to 0 ° C. with stirring.

  After the internal temperature reached 0 ° C., 101.3 g (0.66 mol) of trifluoromethanesulfonic acid fluoride was introduced over 60 minutes through a gas blowing tube. At this time, exotherm occurred and the reaction temperature rose to 5 ° C. The maximum pressure was 0.05 MPa. After the introduction, the temperature was raised to room temperature over 30 minutes with stirring, and stirring was further performed for 3 hours. The pressure at this time was 0.02 MPa.

  After the stirring was completed, the residual pressure of trifluoromethanesulfonic acid fluoride was removed, and the contents in the autoclave were taken out. 300 g of clean water was added to the reaction mixture, and the mixture was stirred for 30 minutes and then separated into two layers. The aqueous layer was removed, dilute sulfuric acid (a mixture of 10 g of sulfuric acid and 300 g of clean water) was added and stirred for 30 minutes, and the two layers were separated to remove the aqueous layer. Further, sodium bicarbonate water (a solution in which 10 g of sodium hydrogen carbonate was dissolved in 300 g of tap water) was added, and the same operation was performed to obtain an organic layer.

  After distilling off the solvent under reduced pressure, the resulting crude product is dissolved in a mixed solvent of isopropyl ether and heptane by heating and cooling, and crystallization is performed by cooling, and the resulting crystals are filtered and dried. 67 g of 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. When the composition was examined by gas chromatography, the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 99%. The yield was 43%.

  As described above, in this comparative example, a mixed solvent of acetonitrile and isopropyl ether was used, and the reaction vessel was hermetically sealed and pressurized, and “reaction at 0 ° C. or higher” was attempted. However, no significant yield improvement was observed compared to the reaction at normal pressure (Comparative Example 1).

[Reference Example 1]
350 g of acetonitrile, 70.7 g (0.699 mol) of triethylamine, 33.1 g of 2-aminoethyl 2-methylacrylate hydrochloride (0.200 mol), polymerization prohibited in a 1 L three-necked flask equipped with a thermometer, reflux condenser and calcium chloride tube 0.2 g of phenothiazine was added as an agent and the mixture was cooled to −30 ° C. with stirring.

  After the internal temperature reached −30 ° C., 36.5 g (0.240 mol) of trifluoromethanesulfonic acid fluoride was introduced into the slurry as a gas over one hour. After completion of the introduction, the mixture was further stirred for 1 hour and then warmed to room temperature.

  Solvent acetonitrile and unreacted trifluoromethanesulfonic acid fluoride were distilled off from the reaction solution under reduced pressure. 1 L of diisopropyl ether was added to form a suspension, and the precipitated triethylamine hydrochloride and triethylamine fluoride were separated by filtration. To the filtrate, 200 mL of 18% aqueous calcium chloride solution was added, washed and separated into two layers, and the organic layer was further washed with 200 g of 10% aqueous sodium chloride three times. The organic layer was dried over 40 g of magnesium sulfate, and after removing the magnesium sulfate by filtration, 0.2 g of phenothiazine was added and the solvent was distilled off. As a result, 44.2 g of crude organic matter was obtained.

  The crude organic material was distilled under reduced pressure, and a fraction of 105 to 115 ° C./13 Pa was collected. As a result, 36.0 g of 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. When the composition was examined by gas chromatography, the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 97%.

  The obtained organic substance was dissolved by heating in a mixed solvent of diisopropyl ether and n-hexane, and crystallization was performed by cooling to obtain 32.4 g of white crystals. When the composition was examined by gas chromatography, the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 99.0%. The yield was 61%.

  Thus, even if it is in an acetonitrile solvent, if the strong cooling condition of −30 ° C. is adopted, it is possible to obtain the target product with a good yield.

[Reference Example 2]
350 g of acetonitrile, 70.7 g (0.699 mol) of triethylamine, 33.1 g (0.200 mol) of 2-aminoethyl 2-methyl acrylate hydrochloride, 0.2 g of phenothiazine in a 1 L three-necked flask equipped with a thermometer, reflux condenser and calcium chloride tube g was added and cooled to −30 ° C. with stirring. After the internal temperature reached −30 ° C., trifluoromethanesulfonic acid chloride 40.3 (0.239 mol) was introduced into the slurry by gas over 1 hour. After completion of the introduction, the mixture was further stirred for 1 hour and then warmed to room temperature. Solvent acetonitrile and unreacted trifluoromethanesulfonic acid chloride were distilled off from the reaction solution under reduced pressure. 1 L of diisopropyl ether was added to form a suspension, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was washed 3 times with 200 g of a 10% aqueous sodium chloride solution.

  The organic layer was dried over 40 g of magnesium sulfate, and after removing the magnesium sulfate by filtration, 0.2 g of phenothiazine was added and the solvent was distilled off. As a result, 22.5 g of crude organic matter was obtained. This crude organic substance was distilled under reduced pressure, and a fraction of 105 to 115 ° C./13 Pa was collected. As a result, 9.9 g of 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate was obtained. When the composition was examined by gas chromatography, the target product, 2-{[(trifluoromethyl) sulfonyl] amino} ethyl 2-methyl acrylate, was 98.0%. The yield was 19%.

  In this reference example, acetonitrile is used as the solvent, the reaction is performed at −30 ° C., and the target product is isolated. However, the yield is low because trifluoromethanesulfonic acid chloride having low reactivity is used as a raw material.

[Reference Example 3]
The reaction was carried out under exactly the same conditions as in Comparative Example 1 (that is, from 0 ° C. to room temperature) except that a mixed solvent of “methylene chloride / acetonitrile” (each amount based on the substrate was 200% by weight) was employed as the solvent.

  As a result, the target product was obtained with a yield of 61%. Thus, it can be seen that if a solvent called methylene chloride is employed, the target product can be obtained in a high yield even when the reaction is carried out at a temperature of 0 ° C. or higher.

  The results of Examples 1 to 6, Comparative Examples 1 and 2, and Reference Examples 1 to 3 are summarized in Table 1.

Claims (9)

Aminoethyl α-substituted acrylate represented by the general formula [1a]

A fluorine-containing alkylsulfonic acid fluoride represented by the general formula [2]

Or a salt of aminoethyl α-substituted acrylate represented by the general formula [1b]

Is reacted with a fluorine-containing alkylsulfonic acid fluoride represented by the general formula [2] in the presence of a base, and a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate represented by the general formula [3]

A method of manufacturing
A method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate, wherein the reaction is carried out using a fluorine-containing compound as a solvent.
[Wherein R ¹ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a difluoromethyl group, a trimethyl group, A fluoromethyl group or a perfluoroethyl group, R ² is a fluorine-containing alkyl group having 1 to 6 carbon atoms, X ⁿ⁻ is a counter anion (where n is a positive integer), and Y is fluorine An atom, a chlorine atom, or a bromine atom. ] The production of fluorine-containing alkylsulfonylaminoethyl α-substituted acrylates according to claim 1, wherein the fluorine-containing compound is a compound having one or more trifluoromethyl groups. Method. The fluorine-containing compound according to claim 1, wherein the fluorine-containing compound is 1,1,2-trichloro-2,2-difluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,1,2-trichloro-2-fluoroethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 2-chloro-1,1,2-trifluoroethyl = ethyl = Ether, 2-chloro-1,1,2-trifluoroethyl = methyl = ether, ethyl = 1,1,2,2-tetrafluoroethyl = ether, 1,1,3,3,3-pentafluoropropyl = Methyl = ether, heptafluoropropyl = 1,2,2,2-tetrafluoroethyl = ether, 1,1,1,2,3,3-hexafluoropropyl = methyl = ether, 1,1,1,2, 3,3-hexafluoropropyl = 2,2,2-trifluoroethyl ether, 1- (methoxy) nonafluorobutane, 1- (ethoxy) nonafluorobutane, methyl trifluoroacetate, trifluoroacetic acid Chill, n-butyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, methyl perfluoropentanoate, ethyl perfluoropentanoate, methyl perfluoroheptanoate, ethyl perfluoroheptanoate, methyl perfluorooctanoate , Ethyl perfluorooctanoate, methyl perfluorononanoate, ethyl perfluorononanoate, methyl 2,3,3,3-tetrafluoropropionate, ethyl 2,3,3,3-tetrafluoropropionate, acetic acid 2, 2,2-trifluoromethyl, butanoic acid 2,2,2-trifluoromethyl, trifluoromethylbenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, 2,4-dichloro Benzotrifluoride, fluorobenzene, 1,2-difluorobenzene, 1,3-difluor Lobenzene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, pentafluorobenzene, hexafluorobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 1,2-dichlorohexafluorocyclobutane Perfluorodimethylcyclobutane, 1,2-dichlorohexafluorocyclopent-1-ene, 1,1,2,2,3,3,4-heptafluorocyclopentane, octafluorocyclopentane, perfluoromethylcyclohexane, Fluoro-1,2-dimethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoroethyldimethylcyclohexane, perfluoroalkane compounds represented by the following formula

(Where x is an integer of 4 to 20) and a perfluoroalkylamine compound represented by the following formula:

(Wherein y is an integer of 1 to 20), the fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to claim 1, which is at least one compound selected from the group consisting of Manufacturing method. The method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to any one of claims 1 to 3, wherein the temperature of the reaction is -25 ° C to 50 ° C. 5. The inclusion according to claim 1, wherein the amount of the fluorine-containing compound used as a solvent is 0.05 to 20 g based on 1 g of aminoethyl α-substituted acrylate or aminoethyl α-substituted acrylate salt. A method for producing fluorine alkylsulfonylaminoethyl α-substituted acrylates. Base consists of trimethylamine, triethylamine, N, N-diethylmethylamine, tripropylamine, tributylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide The method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to any one of claims 1 to 5, which is at least one base selected from the group. The method for producing a fluorinated alkylsulfonylaminoethyl α-substituted acrylate according to any one of claims 1 to 6, wherein R ¹ is a methyl group and R ² is a trifluoromethyl group. The fluorine-containing alkylsulfonylaminoethyl α according to any one of claims 1 to 7, characterized in that, in addition to the fluorine-containing compound, a "solvent not containing a fluorine atom" coexists as a solvent. -Manufacturing method of substituted acrylates. "A solvent not containing a fluorine atom" is at least selected from the group consisting of acetonitrile, benzonitrile, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, dimethylsulfoxide, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, triethylamine, and pyridine. The method for producing a fluorine-containing alkylsulfonylaminoethyl α-substituted acrylate according to claim 8, which is one kind of compound.